CN113861557A - Antibacterial and antiviral low-emission modified polypropylene material and preparation method and application thereof - Google Patents
Antibacterial and antiviral low-emission modified polypropylene material and preparation method and application thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 109
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 105
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 78
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 57
- 230000000840 anti-viral effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 88
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 88
- 239000000314 lubricant Substances 0.000 claims abstract description 40
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- 238000003756 stirring Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 21
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- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
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- 229920001577 copolymer Polymers 0.000 claims description 10
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 9
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- 239000002243 precursor Substances 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
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- 239000000178 monomer Substances 0.000 claims description 4
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- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 3
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention particularly relates to an antibacterial and antiviral low-emission modified polypropylene material, and a preparation method and application thereof, belonging to the technical field of polypropylene materials, wherein the modified polypropylene material comprises the following raw materials in parts by mass: 100 parts of polypropylene, 1-10 parts of modified hollow spherical nano cuprous oxide, 5-40 parts of filler, 5-10 parts of toughening agent, 4-8 parts of compatilizer and 1-2 parts of auxiliary agent; the modified hollow spherical nano cuprous oxide is prepared from hollow spherical nano cuprous oxide and a lubricant; the adopted hollow spherical nano cuprous oxide has remarkable antibacterial and antiviral effects, and the cost is lower while the antibacterial and antiviral effects are realized by using the carrier and the silver ion antibacterial agent, so that the material cost control requirement for vehicles can be met.
Description
Technical Field
The invention belongs to the technical field of polypropylene materials, and particularly relates to an antibacterial and antiviral low-emission modified polypropylene material as well as a preparation method and application thereof.
Background
With the continuous increase of automobile keeping quantity in China, the daily life of automobiles and people is increasingly close, and meanwhile, the smell and the air quality in the automobiles are more and more concerned by consumers. In recent years, due to the continuous development and innovation of automobile lightweight technology, plastics have been widely used for interior and exterior parts of automobile bodies, particularly modified polypropylene materials, and are widely used for large interior parts such as instrument panels, door shields, sub-instrument panels, and the like. When the temperature in the vehicle rises, volatile organic compounds in the polypropylene material can be released, and odor and VOC are generated in the closed vehicle, so that the body of passengers in the vehicle is damaged.
In addition, the new crown epidemic situation which is suddenly seen in 2020 makes people pay more attention to the health of the people, and as an automobile which is frequently contacted with the automobile, the environment which is closed by a cabin provides a favorable environment for the mass propagation and growth of bacteria and viruses. A communication from American scientists (Correspondence) was published in The New England Journal of Medicine, and The survival time of The New coronavirus (SARS-CoV-2) in aerosols and on various environmental surfaces was investigated. The results show that the new coronavirus with infectivity can exist for 72 hours on the surface of the plastic. Throughout the country and abroad, the new crown epidemic situation may coexist with human beings for a long time, and due to the complexity of passenger sources in automobiles, the development of materials for antibacterial and antiviral use in automobile interior and effective reduction of raw material odor and VOC is necessary.
In the prior patents which disclose and can be found about the antibacterial low-emission material, the odor and VOC of a polypropylene material are reduced, namely, the method comprises the steps of improving an extrusion process and adding post-baking treatment; and the other method is to add a deodorant or adsorbent into the formula system to realize the adsorption of odor and VOC substances. These approaches add complexity to the process or can only achieve a single effect. In order to achieve the antibacterial effect, inorganic antibacterial agents are usually added, for example, in the method disclosed in chinese patent application CN 111471234A, carriers such as zeolite are combined with phosphate carriers, and metal silver ions are compounded to achieve the antibacterial effect, and the antibacterial effect is not claimed. The cost is high by adopting the silver ion antibacterial agent. Therefore, how to realize the antibacterial and antiviral effects and effectively reduce the odor, VOC and cost of raw materials has important practical significance.
Disclosure of Invention
The application aims to provide an antibacterial and antiviral low-emission modified polypropylene material, and a preparation method and application thereof, so as to solve the problem of high cost of realizing an antibacterial function of the existing automotive interior material.
The embodiment of the invention provides an antibacterial and antiviral low-emission modified polypropylene material, which comprises the following raw materials in parts by mass: 100 parts of polypropylene, 1-10 parts of modified hollow spherical nano cuprous oxide, 5-40 parts of filler, 5-10 parts of toughening agent, 4-8 parts of compatilizer and 1-2 parts of auxiliary agent; the modified hollow spherical nano cuprous oxide is prepared from hollow spherical nano cuprous oxide and a lubricant.
Optionally, the mass ratio of the hollow spherical nano cuprous oxide to the lubricant is 60-80: 20-40.
Optionally, the opening ratio of the hollow spherical nano cuprous oxide is 10% -30%, and the particle size of the hollow spherical nano cuprous oxide is 80nm-150 nm.
Optionally, the lubricant comprises a silane coupling agent and/or white mineral oil.
Optionally, the filler comprises one of talc, calcium carbonate, kaolin, mica and whiskers;
the toughening agent comprises an ethylene-octene copolymer and/or an ethylene-propylene copolymer;
the compatibilizer comprises maleic anhydride grafted polypropylene;
the auxiliary agent comprises an antioxidant and/or a light stabilizer, the antioxidant comprises at least one of triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-toluene phenyl) acrylate, tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and tris (2, 4-di-tert-butylphenol) phosphite, and the light stabilizer comprises a BW-6911 type light stabilizer.
Optionally, the grafting ratio of the maleic anhydride grafted polypropylene is 0.7% -1.5%.
Optionally, the polypropylene comprises high-crystalline homo-polypropylene and/or co-polypropylene, the crystallinity of the polypropylene is more than or equal to 70%, the isotacticity of the polypropylene is more than 95%, and the melt index of the polypropylene is 1g/10min-80g/10 min.
Optionally, the mass content of the ethylene monomer in the copolymerized polypropylene is not more than 15%.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the antibacterial and antiviral low-emission modified polypropylene material, which comprises the following steps:
mixing the hollow spherical nano cuprous oxide with a lubricant, and then stirring and dispersing to obtain modified hollow spherical nano cuprous oxide;
mixing polypropylene, modified hollow spherical nano cuprous oxide, a filler, a toughening agent, a compatilizer and an auxiliary agent to obtain a modified polypropylene material precursor;
and extruding the modified polypropylene material precursor to obtain the modified polypropylene material.
Based on the same inventive concept, the embodiment of the invention also provides an application of the antibacterial and antiviral low-emission modified polypropylene material, wherein the application comprises the step of using the modified polypropylene material for preparing automotive upholsteries, and the modified polypropylene material is the modified polypropylene material.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the modified polypropylene material with low antibacterial and antiviral emission provided by the embodiment of the invention comprises the following raw materials in parts by mass: 100 parts of polypropylene, 1-10 parts of modified hollow spherical nano cuprous oxide, 5-40 parts of filler, 5-10 parts of toughening agent, 4-8 parts of compatilizer and 1-2 parts of auxiliary agent; the modified hollow spherical nano cuprous oxide is prepared from hollow spherical nano cuprous oxide and a lubricant; the adopted hollow spherical nano cuprous oxide has remarkable antibacterial and antiviral effects, and the cost is lower while the antibacterial and antiviral effects are realized by using the carrier and the silver ion antibacterial agent, so that the material cost control requirement for vehicles can be met.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a flow chart of a method provided by an embodiment of the invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the applicant finds in the course of the invention that: the nano cuprous oxide has unique structure and good antibacterial performance. The hollow spherical nano cuprous oxide with the opening rate of 10-30 percent has an ultra-large specific surface area and has strong adsorption capacity on small molecular substances. The nano cuprous oxide has stronger oxidability and reducibility to volatile organic compounds such as formaldehyde, and can effectively reduce harmful volatile organic compounds.
According to an exemplary embodiment of the invention, an antibacterial and antiviral low-emission modified polypropylene material is provided, and the modified polypropylene material comprises the following raw materials in parts by mass: 100 parts of polypropylene, 1-10 parts of modified hollow spherical nano cuprous oxide, 5-40 parts of filler, 5-10 parts of toughening agent, 4-8 parts of compatilizer and 1-2 parts of auxiliary agent; the modified hollow spherical nano cuprous oxide is prepared from hollow spherical nano cuprous oxide and a lubricant.
The reason that the hollow spherical nano cuprous oxide has remarkable antibacterial and antiviral effects is that the material cost is optimized on the premise that the antibacterial and antiviral effects are achieved, the reason that the mass part of the modified hollow spherical nano cuprous oxide is controlled to be 1-10 parts is that the material cost is increased, the dispersion of the hollow spherical nano cuprous oxide is not facilitated, the antibacterial and antiviral functions cannot be improved, and the antibacterial and antiviral effects are poor due to the undersized adverse effects.
As an alternative embodiment, the mass ratio of the hollow spherical nano cuprous oxide to the lubricant is 60-80: 20-40.
Controlling the mass ratio of the hollow spherical nano cuprous oxide to the lubricant to be 60-80: the reason for 20-40 is that the lubricant not only has the function of modifying cuprous oxide, but also has the function of dispersing cuprous oxide, and the adverse effect of excessively large mass ratio is that the cuprous oxide content is too high, the cuprous oxide cannot be completely dispersed by the lubricant, and the cuprous oxide cannot be modified, so that the nano cuprous oxide is aggregated, and the antibacterial and antiviral effects and material performance of the material are affected; the adverse effect of too small is that the cuprous oxide content is too low, and the antibacterial and antiviral properties of the dispersed material cannot meet the requirements.
Specifically, the hollow spherical nano cuprous oxide is added into the lubricant according to the proportion, and the mixture is dispersed for 2-4 hours by using a magnetic stirrer, so that the modified hollow spherical nano cuprous oxide is obtained.
As an alternative embodiment, the hollow spherical nano cuprous oxide can be prepared by a chemical deposition method and an electrochemical method, the opening ratio of the hollow spherical nano cuprous oxide is 10% -30%, and the particle size of the hollow spherical nano cuprous oxide is 80nm-150 nm.
The hollow spherical nano cuprous oxide with the opening rate of 10-30 percent has an ultra-large specific surface area and has strong adsorption capacity on small molecular substances. The nano cuprous oxide has stronger oxidability and reducibility to volatile organic compounds such as formaldehyde, and can effectively reduce harmful volatile organic compounds.
The reason for controlling the particle size of the hollow spherical nano cuprous oxide to be 80nm-150nm is that the cuprous oxide has various shapes, the hollow spherical shape with the opening can simultaneously have the function of adsorbing small molecular gas, and the cuprous oxide formed is in the shape of the open hollow spherical shape when the particle size is 80nm-150 nm; the adverse effect of overlarge grain diameter value is that the nano cuprous oxide is flaky, the specific surface area is sharply reduced, the gas adsorption effect is not achieved, the antibacterial and antiviral performance is weakened, the adverse effect of undersize is that totally-enclosed spherical grains are formed, and the gas adsorption effect is not achieved when the opening rate is too small.
As an alternative embodiment, the lubricant comprises a silane coupling agent and/or white mineral oil.
As an alternative embodiment, the filler comprises one of talc, calcium carbonate, kaolin, mica and whiskers; the toughening agent comprises an ethylene-octene copolymer and/or an ethylene-propylene copolymer; the compatilizer comprises maleic anhydride grafted polypropylene; the auxiliary agent comprises an antioxidant and/or a light stabilizer, the antioxidant comprises at least one of triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-toluene phenyl) acrylate, tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and tris (2, 4-di-tert-butylphenol) phosphite, and the light stabilizer comprises a BW-6911 type light stabilizer.
Preferably, the filler is talcum powder with the particle size of 2500 meshes; the octene content of the ethylene-octene copolymer was 25%, and the melt index was 0.5g/10 min.
Preferably, the antioxidant is prepared by mixing tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butylphenol) phosphite ester (antioxidant 168) according to the mass ratio of 1: 2.
As an alternative embodiment, the maleic anhydride grafted polypropylene has a grafting degree of 0.7% to 1.5%.
The reason for controlling the grafting rate of the maleic anhydride grafted polypropylene to be 0.7-1.5% is that the adverse effect of overlarge grafting rate is that the maleic anhydride has a large self-odor, the grafting rate is overlarge, the self-odor intensity of the material is large, and the material does not meet the requirement of using a low-odor material in an automobile, and the adverse effect of undersize is that the polypropylene material, the inorganic filler and the modified nano cuprous oxide have poor compatibility, the material performance is poor, and the good antibacterial and antiviral performance cannot be realized.
Preferably, the grafting ratio of the maleic anhydride grafted polypropylene is 1.2%.
As an alternative embodiment, the polypropylene comprises high-crystallization homo-polypropylene and/or co-polypropylene, the crystallinity of the polypropylene is more than or equal to 70%, the isotacticity of the polypropylene is more than 95%, and the melt index of the polypropylene is 1g/10min-80g/10 min. Wherein the mass content of the ethylene monomer in the copolymerized polypropylene is not more than 15 percent.
Preferably, the polypropylene has a crystallinity of 75% and a melt index of between 20 and 45g/10 min.
According to another exemplary embodiment of the present invention, there is provided a method for preparing an antibacterial and antiviral low-emission modified polypropylene material, the method comprising:
s1, mixing hollow spherical nano cuprous oxide with a lubricant, and then stirring and dispersing to obtain modified hollow spherical nano cuprous oxide;
specifically, the weight ratio of the hollow spherical nano cuprous oxide to the lubricant is 60-80: and (3) adding the hollow spherical nano cuprous oxide into the lubricant according to the proportion of 20-40, and dispersing for 2-4 hours by adopting a magnetic stirrer to obtain the modified hollow spherical nano cuprous oxide.
S2, mixing polypropylene, modified hollow spherical nano cuprous oxide, a filler, a toughening agent, a compatilizer and an auxiliary agent to obtain a modified polypropylene material precursor;
specifically, the polypropylene, the mixture I, the filler, the toughening agent, the compatilizer and the auxiliary agent are sequentially added into a mixing device according to the formula, and are stirred and uniformly mixed to obtain the modified polypropylene material precursor, wherein the adopted mixing device is a stirring barrel or a high-speed mixer, the mixing time is 5-10 minutes, and the stirring speed is 500-1200 revolutions per minute.
And S3, carrying out extrusion treatment on the modified polypropylene material precursor to obtain the modified polypropylene material.
Specifically, the modified polypropylene composite material precursor is placed into extrusion equipment for extrusion treatment, and the antibacterial and antiviral low-emission modified polypropylene material is obtained, wherein the adopted extrusion equipment is a two-section vacuum double-screw extruder, and the modified polypropylene material precursor is extruded and granulated in a molten state. In this example, the types of extruders used were: () The specific extrusion process conditions are as follows: the temperature of the first zone is 170-180 ℃, the temperature of the second zone is 180-190 ℃, the temperature of the third zone is 190-200 ℃, the temperature of the fourth zone is 180-190 ℃, the temperature of the fifth zone is 165-175 ℃, the rotation speed of the extrusion equipment is 350-400 r/min, the vacuum degree of the two zones is-0.05-0.08 MPa, and the extrusion treatment time is 1-3 min.
The antibacterial and antiviral low-emission modified polypropylene material, the preparation method and the application thereof will be described in detail below with reference to examples, comparative examples and experimental data.
In the following embodiment, the hollow spherical nano cuprous oxide can be prepared by a chemical deposition method and an electrochemical method, and has an opening rate of 10% -30% and a particle size of 80-150 nm.
The polypropylene is one or a mixture of high-crystalline homo-polypropylene or co-polypropylene, and the crystallinity is more than 70%; the isotacticity is more than 95 percent, and the melt index is between 1 and 80g/10 min; the content of ethylene monomer in the copolymerized polypropylene is not more than 15 percent; preferably, the degree of crystallinity is 75% and the melt index is between 20 and 45g/10 min.
The lubricant is selected from one or more of silane coupling agent and white mineral oil. The manufacturer of the silane coupling agent is a Beijing Boride chemical product company Limited, and the mark is KH-570; the white oil was manufactured by kramayi petrochemicals, Xinjiang, under the designation KN 4006. Preferably, the lubricant is formed by mixing a silane coupling agent and white mineral oil according to the mass ratio of 1: 1.
The toughening agent is one of ethylene-octene copolymer (POE), ethylene-propylene copolymer, or mixture thereof; preferably, the ethylene-octene copolymer has an octene content of 25% and a melt index of 0.5g/10 min.
The compatilizer is low-odor high-efficiency maleic anhydride grafted polypropylene, and the grafting rate is 0.7-1.5%; preferably, the grafting yield is 1.2%.
The auxiliary agent is one or the mixture of an antioxidant and a light stabilizer. The antioxidant is one or more selected from triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-toluene phenyl) acrylate, tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butylphenol) phosphite ester (antioxidant 168). The light stabilizer is BW-6911. Preferably, the auxiliary agent is formed by mixing an antioxidant 1010, an antioxidant 168 and a light stabilizer in a mass ratio of 1:2: 1.
Example 1
The preparation method of the antibacterial and antiviral low-emission modified polypropylene material comprises the following steps: mixing hollow spherical nano cuprous oxide which is prepared by a chemical deposition method and an electrochemical method and has an opening rate of 10-30% and a particle size of 80-150nm with a lubricant according to a mass ratio of 80:20, and dispersing for 2 hours at normal temperature by using a magnetic stirrer to obtain a mixture I in which the lubricant and the hollow spherical nano cuprous oxide are uniformly mixed, wherein the lubricant is a silane coupling agent.
Placing 100 parts of polypropylene, 1 part of mixture I, 5 parts of filler, 5 parts of toughening agent, 4 parts of compatilizer and 1 part of auxiliary agent in a stirring barrel in sequence according to parts by mass, and stirring for 10 minutes, wherein the rotating speed of the stirring barrel is 500 revolutions per minute; wherein the auxiliary agent is antioxidant triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-toluene phenyl) acrylate.
And finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the following steps: the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 200 ℃, the fourth zone is 190 ℃, the fifth zone is 175 ℃, the screw rotation speed is 400 r/min, the two-stage vacuum degree is-0.08 MPa, and the extrusion treatment time is 3 minutes.
Example 2
The preparation method of the antibacterial and antiviral low-emission modified polypropylene material comprises the following steps: mixing hollow spherical nano cuprous oxide which is prepared by a chemical deposition method and an electrochemical method and has an opening rate of 10-30% and a particle size of 80-150nm with a lubricant according to a mass ratio of 80:20, and dispersing for 4 hours at normal temperature by using a magnetic stirrer to obtain a mixture I in which the lubricant and the hollow spherical nano cuprous oxide are uniformly mixed, wherein the lubricant is white mineral oil.
Placing 100 parts of polypropylene, 5 parts of mixture I, 10 parts of filler, 8 parts of toughening agent, 4 parts of compatilizer and 1 part of auxiliary agent in a stirring barrel in sequence according to parts by mass, and stirring for 5 minutes, wherein the rotating speed of the stirring barrel is 1200 revolutions per minute; wherein the auxiliary agent is a BW-6911 type light stabilizer.
And finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the following steps: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 200 ℃, the fourth zone is 180 ℃, the fifth zone is 165 ℃, the screw rotating speed is 350 r/min, the two-stage vacuum degree is-0.05 MPa, and the extrusion processing time is 1 minute.
Example 3
The preparation method of the antibacterial and antiviral low-emission modified polypropylene material comprises the following steps: mixing hollow spherical nano cuprous oxide which is prepared by a chemical deposition method and an electrochemical method and has an opening rate of 10-30% and a particle size of 80-150nm with a lubricant according to a mass ratio of 60:40, and dispersing for 3 hours at normal temperature by using a magnetic stirrer to obtain a mixture I in which the lubricant and the hollow spherical nano cuprous oxide are uniformly mixed, wherein the lubricant is a mixture of a silane coupling agent and white mineral oil according to a mass ratio of 1: 1.
Placing 100 parts of polypropylene, 10 parts of mixture I, 20 parts of filler, 10 parts of toughening agent, 4 parts of compatilizer and 1 part of auxiliary agent in a stirring barrel in sequence according to parts by mass, and stirring for 10 minutes, wherein the rotating speed of the stirring barrel is 800 revolutions per minute; wherein the auxiliary agent is an antioxidant and is prepared by mixing tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butylphenol) phosphite ester (antioxidant 168) according to the mass ratio of 1: 2.
And finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the steps of 170 ℃ in the first zone, 180 ℃ in the second zone, 190 ℃ in the third zone, 180 ℃ in the fourth zone, 175 ℃ in the fifth zone, the rotating speed of a screw is 400 r/min, the vacuum degree of the two zones is-0.08 MPa, and the extrusion treatment time is 3 minutes.
Example 4
The preparation method of the antibacterial and antiviral low-emission modified polypropylene material comprises the following steps: mixing hollow spherical nano cuprous oxide which is prepared by a chemical deposition method and an electrochemical method and has an opening rate of 10-30% and a particle size of 80-150nm with a lubricant according to a mass ratio of 60:40, and dispersing for 3 hours at normal temperature by using a magnetic stirrer to obtain a mixture I in which the lubricant and the hollow spherical nano cuprous oxide are uniformly mixed, wherein the lubricant is a mixture of a silane coupling agent and white mineral oil according to a mass ratio of 1: 1.
Placing 100 parts of polypropylene, 10 parts of mixture I, 30 parts of filler, 8 parts of toughening agent, 8 parts of compatilizer and 2 parts of auxiliary agent in a stirring barrel in sequence according to parts by mass, and stirring for 10 minutes, wherein the rotating speed of the stirring barrel is 800 revolutions per minute; wherein the auxiliary agent is formed by mixing an antioxidant 1010, an antioxidant 168 and a light stabilizer according to the mass ratio of 1:2: 1.
And finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the following steps: the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 200 ℃, the fourth zone is 190 ℃, the fifth zone is 175 ℃, the screw rotation speed is 400 r/min, the two-stage vacuum degree is-0.08 MPa, and the extrusion treatment time is 3 minutes.
Example 5
The preparation method of the antibacterial and antiviral low-emission modified polypropylene material comprises the following steps: mixing hollow spherical nano cuprous oxide which is prepared by a chemical deposition method and an electrochemical method and has an opening rate of 10-30% and a particle size of 80-150nm with a lubricant according to a mass ratio of 80:20, and dispersing for 3 hours at normal temperature by using a magnetic stirrer to obtain a mixture I in which the lubricant and the hollow spherical nano cuprous oxide are uniformly mixed, wherein the lubricant is a mixture of a silane coupling agent and white mineral oil according to a mass ratio of 1: 1.
Placing 100 parts of polypropylene, 10 parts of mixture I, 40 parts of filler, 8 parts of toughening agent, 8 parts of compatilizer and 2 parts of auxiliary agent in a stirring barrel in sequence according to parts by mass, and stirring for 10 minutes, wherein the rotating speed of the stirring barrel is 800 revolutions per minute; wherein the auxiliary agent is an antioxidant and is prepared by mixing tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butylphenol) phosphite ester (antioxidant 168) according to the mass ratio of 1: 2.
And finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the following steps: the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 200 ℃, the fourth zone is 190 ℃, the fifth zone is 175 ℃, the screw rotation speed is 400 r/min, the two-stage vacuum degree is-0.08 MPa, and the extrusion treatment time is 3 minutes.
Comparative example 1
The preparation method of the modified polypropylene composite material of the comparative example comprises the following steps: placing 100 parts of polypropylene, 10 parts of lubricant, 40 parts of filler, 8 parts of toughening agent, 8 parts of compatilizer and 2 parts of auxiliary agent in a stirring barrel in sequence, and stirring for 10 minutes, wherein the rotating speed of the stirring barrel is 800 revolutions per minute; and finally, extruding and granulating the mixed raw materials by a double-screw extruder, wherein the extrusion process comprises the following steps: the first zone is 170 ℃, the second zone is 180 ℃, the third zone is 200 ℃, the fourth zone is 190 ℃, the fifth zone is 175 ℃, the screw rotation speed is 400 r/min, the two-stage vacuum degree is-0.08 MPa, and the extrusion treatment time is 3 minutes.
Examples of the experiments
The antibacterial and antiviral low-emission modified polypropylene materials prepared in examples 1 to 5 and comparative example 1 and the modified polypropylene composite material prepared in the comparative example were dried in an oven at 80 to 90 ℃ for 2 hours, and then the dried particulate material was injection molded into a standard test bar on an injection molding machine, and the test bar was subjected to in-out test, and the test results are shown in the following table:
| index (I) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Tensile Strength (MPa) | 23 | 25 | 28 | 30 | 32 | 29 |
| Flexural modulus (MPa) | 1700 | 1950 | 2100 | 2350 | 2500 | 2300 |
| Smell (grade) | 2.5 | 2.4 | 2.2 | 2.3 | 2.0 | 3.2 |
| TVOC(mg/kg) | 15.63 | 8.39 | 2.72 | 3.19 | 0.82 | 75.93 |
| Antibacterial ratio (%) | 89.5 | 90.4 | 96.8 | 96.3 | 99.9 | 60.2 |
| Rate of virus inactivation (%) | 88.35 | 91.68 | 97.29 | 95.62 | 98.79 | 49.4 |
In the table, the tensile strength was measured according to ISO 527-2 standard, sample type 1A, tensile speed 50 mm/min;
the flexural modulus was measured according to ISO 178 and the bending speed was 2 mm/min.
The odor test was performed according to EQCL-64 standard. The sample in 1L closed container was stored at 80 deg.C for 2 hours, taken out and cooled at 23 deg.C for 1 hour, and then rated according to the EQCL-64 standard, with 5 ginseng evaluation, to give a statistical total rating: grade 1 is imperceptible, grade 2 is mild intensity, grade 3 is moderate intensity, grade 4 is strong, grade 5 is strong, and grade 6 is intolerable. A rating score of less than or equal to 2.6 is acceptable.
The TVOC is detected according to the EQCT-1653 standard, and the TVOC is qualified when the TVOC is less than 50 mg/kg.
The antibacterial test is carried out according to the standard of GB/T31402-2015 method for testing antibacterial performance of plastic surfaces.
The antivirus test is carried out by contacting SARS-CoV-2 virus stock solution with antibacterial antivirus modified polypropylene material, incubating for 1h, detecting virus titer, and calculating virus inactivation rate.
The table shows that the introduction of the hollow spherical nano cuprous oxide with the aperture opening ratio of 10-30% effectively adsorbs small molecular substances in the modified polypropylene, and effectively reduces the odor and TVOC of the modified polypropylene material. The higher the content of the hollow spherical nano cuprous oxide is, the better the emission characteristic of the modified polypropylene is, and the optimal smell is only 2.0 grade, and the smell can not be detected basically. In addition, the modified polypropylene material containing the hollow spherical nano cuprous oxide has obvious antibacterial and antiviral effects, and the antibacterial rate and the virus inactivation rate are increased along with the increase of the content of the hollow spherical nano cuprous oxide. According to the embodiment, the lubricant and the hollow-core nano cuprous oxide are mixed by using the magnetic stirrer, so that the surface activity of the hollow-core spherical nano cuprous oxide can be enhanced, and the core spherical nano cuprous oxide can be simply, quickly and effectively dispersed; the tensile strength and the flexural modulus of the modified polypropylene material can be improved by the uniformly dispersed hollow spherical cuprous oxide nanoparticles, which also shows that the interface bonding strength of the hollow spherical cuprous oxide nanoparticles and the polypropylene is improved by the mixing process, so that the modified polypropylene material with the characteristics of antibiosis, antivirus, excellent performance and excellent material appearance is prepared.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) the hollow spherical nano cuprous oxide adopted by the modified polypropylene material provided by the embodiment of the invention has remarkable antibacterial and antiviral effects, meanwhile, the opening rate is 10-30% to play a role in odor adsorption, the nano cuprous oxide has strong oxidability and reducibility to volatile organic compounds such as formaldehyde, and can effectively reduce harmful volatile organic compounds, and the material has excellent appearance and can be widely applied to the fields of automotive interior appearance and non-appearance parts;
(2) the modified polypropylene material provided by the embodiment of the invention adopts the combination of the lubricant and the hollow spherical nano cuprous oxide by adopting a magnetic stirring mode, solves the problem of the dispersibility of the hollow spherical nano cuprous oxide, improves the interface bonding strength of the hollow spherical nano cuprous oxide and polypropylene, and has simple adopted dispersing equipment and process and easy operation;
(3) the modified polypropylene material provided by the embodiment of the invention adopts the hollow spherical nano cuprous oxide, realizes antibacterial and antiviral effects and is low in cost compared with an antibacterial agent using a carrier and silver ions, and can meet the cost control requirement of materials for vehicles.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The antibacterial and antiviral low-emission modified polypropylene material is characterized by comprising the following raw materials in parts by mass: 100 parts of polypropylene, 1-10 parts of modified hollow spherical nano cuprous oxide, 5-40 parts of filler, 5-10 parts of toughening agent, 4-8 parts of compatilizer and 1-2 parts of auxiliary agent; the modified hollow spherical nano cuprous oxide is prepared from hollow spherical nano cuprous oxide and a lubricant.
2. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 1, wherein the mass ratio of the hollow spherical nano cuprous oxide to the lubricant is 60-80: 20-40.
3. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 1, wherein the aperture ratio of the hollow spherical cuprous oxide nanoparticles is 10% -30%, and the particle size of the hollow spherical cuprous oxide nanoparticles is 80-150 nm.
4. The antibacterial and antiviral low-emission modified polypropylene material according to claim 1, wherein the lubricant comprises a silane coupling agent and/or white mineral oil.
5. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 1, wherein the filler comprises one of talc, calcium carbonate, kaolin, mica and whiskers;
the toughening agent comprises an ethylene-octene copolymer and/or an ethylene-propylene copolymer;
the compatibilizer comprises maleic anhydride grafted polypropylene;
the auxiliary agent comprises an antioxidant and/or a light stabilizer, the antioxidant comprises at least one of triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-toluene phenyl) acrylate, tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester and tris (2, 4-di-tert-butylphenol) phosphite, and the light stabilizer comprises a BW-6911 type light stabilizer.
6. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 5, wherein the grafting ratio of the maleic anhydride grafted polypropylene is 0.7-1.5%.
7. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 1, wherein the polypropylene comprises high-crystalline homo-polypropylene and/or co-polypropylene, the crystallinity of the polypropylene is greater than or equal to 70%, the isotacticity of the polypropylene is greater than 95%, and the melt index of the polypropylene is 1g/10min-80g/10 min.
8. The antibacterial and antiviral low-emission modified polypropylene material as claimed in claim 7, wherein the content of ethylene monomer in the co-polypropylene is not more than 15% by mass.
9. A preparation method of an antibacterial and antiviral low-emission modified polypropylene material is characterized by comprising the following steps:
mixing the hollow spherical nano cuprous oxide with a lubricant, and then stirring and dispersing to obtain modified hollow spherical nano cuprous oxide;
mixing polypropylene, modified hollow spherical nano cuprous oxide, a filler, a toughening agent, a compatilizer and an auxiliary agent to obtain a modified polypropylene material precursor;
and extruding the modified polypropylene material precursor to obtain the modified polypropylene material.
10. Use of an antibacterial and antiviral low-emission modified polypropylene material for the preparation of automotive interior trim parts, wherein the modified polypropylene material is the modified polypropylene material according to any one of claims 1 to 8.
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